Marine Gas hydrate research: Changing views over the past 25 years

During the past quarter century views have changed in marine gas-hydrate research and in its perception by the society at large: (1) Deep-sea drilling has gone from a policy of avoiding gas hydrate to emphasizing deliberate drilling for it. (2) International programs have evolved from exploiting gas hydrates as energy to considering exchange of CO2 for CH4 hydrates as a means of carbon dioxide storage. (3) Lately, due to global change, research has changed from pursuing methane-hydrate reserves to documenting release of methane from destabilization in marginal seas. The first stage generated a wealth of knowledge and laid the foundation for marine gas hydrate research upon which we build today. The second stage is traced to more accurately estimating exploitable hydrate-bound gas and finding recovery technologies, that has lead to the discovery of an innovative option coupling production of methane from CH4-hydrate to storage of CO2 via in the sub-seafloor. Governments worldwide have recognized the potential for carbon dioxide storage and have begun to implement regulations for such environmentally safe carbon capture and storage (CCS). During the third stage, in further exploring global methane hydrate reserves, it has become evident that environmental changes over the past decades may have triggered release of methane from destabilizing hydrate at the seabed as well as diminished oxygen content in the near-bottom of marginal seas. Such scenarios had been proposed for past global warming and now appear to become active again. Exemplary highlights and selected cases studies are documented for each of the evolving stages

Rising methane gas bubbles form massive hydrate layers at the seafloor

Extensive methane hydrate layers are formed in the near-surface sediments of the Cascadia margin. An undissociated section of such a layer was recovered at the base of a gravity core (i.e. at a sediment depth of 120 cm) at the southern summit of Hydrate Ridge. As a result of salt exclusion during methane hydrate formation, the associated pore waters show a highly elevated chloride concentration of 809 mM. In comparison, the average background value is 543 mM. A simple transport-reaction model was developed to reproduce the Cl- observations and quantify processes such as hydrate formation, methane demand, and fluid flow. From this first field observation of a positive Cl- anomaly, high hydrate formation rates (0.15–1.08 mol cm-2 a-1) were calculated. Our model results also suggest that the fluid flow rate at the Cascadia accretionary margin is constrained to 45–300 cm a-1. The amount of methane needed to build up enough methane hydrate to produce the observed chloride enrichment exceeds the methane solubility in pore water. Thus, most of the gas hydrate was most likely formed from ascending methane gas bubbles rather than solely from CH4 dissolved in the pore water

Fluid Venting Activity on the Costa Rica Margin: New Results from Authigenic Carbonates

Carbonate precipitates on mounds and along tectonic scarps off the Costa Rica margin are manifestations of subduction-induced dewatering. The long-term dewatering history is recorded in mineralogical, petrological and isotope signals of carbonates recovered from these sites. The carbonates are strongly depleted in δ13C (−11 to −53‰ PDB) and enriched in δ18O (+4 to +8‰ PDB). Thermogenic methane and biogenic methane were identified as sources of the carbon. Chemoherm carbonates and seepage-associated carbonates formed in a focused flow regime have lighter δ13C values, while others formed in a more diffusive flow regime have slightly enriched C isotope values. Three fluid components were inferred based on the calculation of equilibrium δ18O: clay dehydration water, gas hydrate water and seawater. Calculated equilibrium δ18O values of carbonates from different down-core depths as well as from different precipitation stages show that the δ18O of the precipitating fluid is progressively depleted with time. Dolostones showing a methane-C source and a well constrained O-isotope signature are thought to have formed at depth in the sediment and subsequently became exhumed. Glauconitic sandstones cemented by methane-derived carbonate provide evidence that fluid and solid material have been expelled by the mud volcano

Volatile halogenated hydrocarbons over the western Pacific between 43° and 4°N

A spectrum of halogenated hydrocarbon compounds in marine air masses were surveyed over an area in the western Pacific between 43°N, 150°E and 4°N, 113°E in September 1994. The ship's track between northern Japan and Singapore traversed three climatic zones of the northern hemisphere. Recently polluted air, clean marine air derived from the central Pacific Ocean from different latitudes, and marine air from the Indonesian archipelago were collected. Tetrachloroethene and trichloroethene of anthropogenic origin, brominated halocarbons as tribromomethane, dibromochloromethane and bromodichloromethane of anthropogenic and natural sources, and other trace gases were measured in the air samples. Very sparse data on the distribution of these compounds exist for the western Pacific atmosphere. The distribution patterns of the compounds were related to synoptic-scale meteorology, spatial conditions, and origin of the air masses. Anthropogenic and natural sources for both chlorinated and brominated substances were identified. Tetrachloroethene and trichloroethene concentrations and their ratios identify anthropogenic sources. Their mixing ratios were quite low compared to previously published data. They are in agreement with expected low concentrations of photochemically active substances during autumn, with an overall decrease in concentrations toward lower latitudes, and with a decrease of emissions during recent years. Strong evidence for a natural source of trichloroethene was discovered in the tropical region. The concentrations of naturally released brominated species were high compared to other measurements over the Pacific. Gradients toward the coasts and elevated concentrations in air masses influenced by coastal emissions point to significant coastal sources of these compounds. The trace gas composition of anthropogenic and natural compounds clearly identified the air masses which were traversed during the cruise

In situ benthic fluxes from an intermittently active mud volcano at the Costa Rica convergent margin

Along the erosive convergent margin off Costa Rica a large number of mound-shaped structures exist built by mud diapirism or mud volcanism. One of these, Mound 12, an intermittently active mud volcano, currently emits large amounts of aqueous dissolved species and water. Chemosynthetic vent communities, authigenic carbonates, and methane plumes in the water column are manifestations of that activity. Benthic flux measurements were obtained by a video-guided Benthic Chamber Lander (BCL) deployed at a vent site located in the most active part of Mound 12. The lander was equipped with 4 independent chambers covering adjacent areas of the seafloor. Benthic fluxes were recorded by repeated sampling of the enclosed bottom waters while the underlying surface sediments were recovered with the lander after a deployment time of one day. One of the chambers was placed directly in the centre of an active vent marked by the occurrence of a bacterial mat while the other chambers were located at the fringe of the same vent system at a lateral distance of only 40 cm. A transport-reaction model was developed and applied to describe the concentration profiles in the pore water of the recovered surface sediments and the temporal evolution of the enclosed bottom water. Repeated model runs revealed that the best fit to the pore water and benthic chamber data is obtained with a flow velocity of 10 cm yr− 1 at the centre of the vent. The flux rates to the bottom water are strongly modified by the benthic turnover (benthic filter). The methane flux from below at the bacterial mat site is as high as 1032 μmol cm− 2 yr− 1, out of which 588 μmol cm− 2 yr− 1 is oxidised in the surface sediments by microbial consortia using sulphate as terminal electron acceptor and 440 μmol cm− 2 yr− 1 are seeping into the overlaying bottom water. Sulphide is transported to the surface by ascending fluids (238 μmol cm− 2 yr− 1) and is formed within the surface sediment by the anaerobic oxidation of methane (AOM, 588 μmol cm− 2 yr− 1). However, sulphide is not released into the bottom water but completely oxidized by oxygen and nitrate at the sediment/water interface. The oxygen and nitrate fluxes into the sediment are high (781 and 700 μmol cm− 2 yr− 1, respectively) and are mainly driven by the microbial oxidation of sulphide. Benthic fluxes were much lower in the other chambers placed in the fringe of the vent system. Thus, methane and oxygen fluxes of only 28 and 89 μmol cm− 2 yr− 1, respectively were recorded in one of these chambers. Our study shows that the aerobic oxidation of methane is much less efficient than the anaerobic oxidation of methane so that methane which is not oxidized within the sediment by AOM is almost completely released into the bottom water. Hence, anaerobic rather than aerobic methane oxidation plays the major role in the regulation of benthic methane fluxes. Moreover, we demonstrate that methane and oxygen fluxes at cold vent sites may vary up to 3 orders of magnitude over a lateral distance of only 40 cm indicating an extreme focussing of fluid flow and methane release at the seafloor